Method and system for producing methanol from inert-rich syngas

ABSTRACT

A method for producing methanol from inert-rich syngas includes installing a catalytic pre-reactor is upstream of the single or mufti-stage synthesis loop, a first part of the syngas being converted to methanol in the catalytic pre-reactor. Furthermore, an inert gas separation stage, for example a pressure swing adsorption system or a membrane system, is connected downstream of the synthesis loop, whereby a hydrogen-enriched syngas stream can be returned to the synthesis loop. In the processing of methane-rich syngas, the inert gas separation stage may also comprise an autothermal reformer in which methane is converted to carbon oxides and hydrogen, which are also returned into the synthesis loop.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a U.S. national phase application under 35 U.S.C.§371 of International Application No. PCT/EP2012/001256, filed on Mar.22, 2012, and claims benefit to German Patent Application No. DE 10 2011017 300.5 filed on Apr. 15, 2011. The international application waspublished in German on Oct. 18, 2012, as WO 2012/139703 A1 under PCTArticle 21(2).

FIELD

This invention relates to a process for the production of methanol andto a plant for carrying out this process. In particular, the inventionrelates to a process for the conversion of synthesis gas with a highcontent of inert components to methanol, as it is obtained for exampleby gasification of natural gas with oxygen-enriched air or bygasification of biomass or coal with a gas containing oxygen. Theinvention furthermore relates to a method for retrofitting an existingplant for the production of methanol from the operation with synthesisgas low in inerts to the operation with synthesis gas rich in inerts.

BACKGROUND

Processes for the production of methanol by catalytic conversion ofsynthesis gas containing hydrogen and carbon oxides have long since beenknown to those skilled in the art. For example in Ullmann's Encyclopediaof Industrial Chemistry, Sixth Edition, 1998 Electronic Release, Chapter“Methanol”, Sub-chapter 5.2 “Synthesis”, various basic processes for theproduction of methanol are described.

A more advanced, two-stage process for the production of methanol isknown for example from EP 0 790 226 B1. The methanol is produced in acyclic process in which a mixture of fresh and partly reacted synthesisgas first is supplied to a water-cooled reactor and then to a gas-cooledreactor, in each of which the synthesis gas is converted to methanol ona copper-based catalyst. The methanol produced in the process isseparated from the synthesis gas to be recirculated, which then iscountercurrently passed through the gas-cooled reactor as coolant andpreheated to a temperature of 220 to 280° C., before it is introducedinto the first synthesis reactor. A part of the synthesis gas to berecirculated is removed from the process as purge stream (so-calledpurge), in order to prevent that inert components are enriched withinthe synthesis cycle. This measure is also taught in the unexaminedGerman Patent Application DE 2934332 A1 and in the European PatentApplication EP 1016643 A1.

In the two methods described above it is disadvantageous that whenprocessing synthesis gases with a high content of inert components thecycle ratio must be increased, as due to the lower partial pressures ofthe reactants the conversion to methanol per passage through thesynthesis reactor is lower than with synthesis gas low in inerts. Thisleads to an increase of the required compressor capacity and—with agiven production capacity for methanol—to larger dimensions forapparatuses and conduits.

Inert components on the one hand are understood to be inorganic gasconstituents such as nitrogen or inert gases, which are obtained forexample from the production of synthesis gas proceeding from natural gaswith corresponding constituents. Such natural gases are obtained forexample from Asian deposits. In the gasification of natural gases withair or oxygen-enriched air, as it is discussed recently above all forsmaller plants which are located far away from air separation systemsfor producing oxygen, there are also obtained synthesis gases rich innitrogen; this is proposed for example in the International PatentApplication WO 96/14279 A1. On the other hand, non-converted methane,which during the gasification of natural gas or coal can be contained inthe synthesis gas product, is regarded as an inert gas in the sense ofthe methanol synthesis, as it is not converted further in thissynthesis.

The problems of processing of synthesis gases rich in inerts in themethanol synthesis have been known for quite some time. Varioustechnical solutions have already been proposed, which could, however,not gain acceptance due to their disadvantages.

In the unexamined German Patent Application DE 1296133 B it is proposed,for example, to treat the raw synthesis gas containing inert componentssuch as nitrogen, methane or argon by a xylene wash, whereby distinctreductions of the contents of the inert components should be achieved.Here, it is disadvantageous that before entry into the gas scrubber thetemperature of the synthesis gas must be lowered to −10 to −30° C., inorder to significantly lower the partial pressures of the inertcomponents. This results in a high loss of energy. In addition, a ladenabsorbent is obtained, which must be aftertreated and which contains thecomponent xylene foreign to the process of the methanol synthesis.

A similar technical teaching can be taken from the unexamined GermanPatent Application DE 10156092 A1, in which it is proposed to provide anabsorption stage upstream of each catalytic reaction system for theproduction of methanol, which contains a methanol synthesis catalyst asabsorbent and which is operated at a temperature which lies below thetemperature for the catalytic conversion to methanol. As absorbent anauxiliary substance inherent to the process is employed, but the twoabove-mentioned disadvantages of a required decrease in temperature andan aftertreatment or disposal of the absorbent still exist.

A method for the production of methanol from a synthesis gas obtainedfrom the autothermal gasification of natural gas, containing 20 to 50 %each of hydrogen, carbon monoxide and methane, is described in thepatent application EP 1819653 A1. There are not taken any particularmeasures with respect to the methane remaining in the reactor product ofthe methanol synthesis reactor, but the hydrogen content is increased bymeans of conversion, the hydrogen—possibly with the likewise producedcarbon dioxide—then is separated and again charged to the methanolsynthesis reactor. The partial pressures of the reactants are increasedby this measure, but the cycle stream remains high due to the highcontent of inert components.

In general, it should therefore be noted that no satisfactory technicalsolution of the object has been found so far, although the problem, asillustrated, already exists for quite some time. In addition, many ofthe above discussed methods aim at reducing the purge stream containinginert components by a corresponding treatment as far as possible.

SUMMARY

In an embodiment, the present invention provides a process for theproduction of methanol from a synthesis gas comprising hydrogen, acarbon oxide, and an inert component, the process comprising: (a)passing a first synthesis gas stream as feed stream through at least onemethanol pre-reactor, in which a part of the carbon oxide iscatalytically converted with hydrogen to obtain methanol; (b) separatingoff the methanol produced in (a) to obtain a second synthesis gasstream; (c) passing the second synthesis gas stream through at least onemethanol main reactor, in which a further part of the carbon oxide iscatalytically converted with hydrogen to obtain methanol; (d) separatingoff the methanol produced in (c) to obtain a third synthesis gas stream;(e) dividing the third synthesis gas stream into a fourth synthesis gasstream and a fifth synthesis gas stream; (f) recirculating the fourthsynthesis gas stream to the methanol main reactor to form an innersynthesis cycle; (g) supplying the fifth synthesis gas stream to atleast one inert gas separation stage, to obtain a sixth stream depletedof inert components and a purge stream enriched in inert components; (g)recirculating the sixth stream to the methanol main reactor to form anouter synthesis cycle.

BRIEF DESCRIPTION OF THE DRAWINGS

The present invention will be described in even greater detail belowbased on the exemplary figures. The invention is not limited to theexemplary embodiments. All features described and/or illustrated hereincan be used alone or combined in different combinations in embodimentsof the invention. The features and advantages of various embodiments ofthe present invention will become apparent by reading the followingdetailed description with reference to the attached drawings whichillustrate the following:

FIG. 1 schematically shows a plant for the production of methanol by aprocess according to the prior art as described above,

FIG. 2 schematically shows a plant for the production of methanolaccording to a first preferred embodiment of the invention,

FIG. 3 schematically shows a plant for the production of methanolaccording to a second preferred embodiment of the invention.

DETAILED DESCRIPTION

In an embodiment, the present invention avoid the above-mentioneddisadvantages and provide a more economic and technically more easilyfeasible process for the production of methanol by using synthesis gasrich in inerts as educt gas, which in particular is characterized by alow energy demand, smaller apparatus dimensions and the avoidance ofauxiliary substances foreign to the process

Surprisingly, it was found that the methanol pre-reactor upstream of themethanol main reactor advantageously cooperates with the methanol mainreactor and the separation of inert synthesis gas components downstreamof the methanol main reactor, because due to the reaction of a part ofthe synthesis gas in the pre-reactor to methanol the gas load of thesynthesis cycle is reduced distinctly. Therefore, the synthesis gascomponents separated from the purge gas stream, the so-called purge, canbe recirculated without a dramatic rise in the required compressorcapacity, the dimensions of the apparatuses and conduits used in thesynthesis cycle, and the amount of catalyst required in the methanolmain reactor.

According to a preferred aspect of the invention it is provided that theinert gas separation stage comprises a pressure swing adsorption systemor a membrane system. In this way, a gas stream enriched in hydrogen andat the same time depleted of inert components can be obtained and berecirculated to the first methanol main reactor.

Advantageously, the inert gas separation stage can comprise anautothermal reformer, preferably along with a pressure swing adsorptionsystem.

The first synthesis gas stream advantageously can be obtained bygasification of natural gas or biomass with a gas containing oxygen.Alternatively, the first synthesis gas stream also can be obtained bygasification of coal with a gas containing oxygen. In the last-mentionedcase, the synthesis gas obtained frequently is particularly rich inmethane, so that in particular in this case it is recommendable that theinert gas separation stage comprises an autothermal reformer, sincemethane is converted in the same and can thus be obtained as synthesisgas.

The methanol streams separated after the methanol pre-reactor or afterthe methanol main reactor or reactors can be supplied, preferablyjointly, to the methanol product processing known per se. The sameusually comprises one or more distillation steps, so that finally puremethanol can be obtained as product.

In a further aspect of the invention, the methanol pre-reactor can beoperated adiabatically or in a cooled, preferably water-cooled manner.In the water-cooled operation of the methanol pre-reactor theexothermicity of the methanol synthesis reaction can be utilized for thesteam generation.

In particular when charging the methanol pre-reactor with low-hydrogensynthesis gases of a low stoichiometric number SN, which is defined by

SN=((c(H₂)−c(CO₂))/((c(CO)+c(CO₂))

the methanol synthesis reaction involves a high release of heat.Therefore, in a further advantageous aspect of the invention it isprovided to equip the methanol pre-reactor with its own synthesis gasrecirculation. After separation of the methanol produced in the methanolpre-reactor, not the entire synthesis gas stream leaving the methanolpre-reactor, but merely a partial stream therefore is guided to themethanol main reactor and the remaining part of the synthesis gas streamis recirculated to before the methanol pre-reactor. In this way, theexothermicity of the conversion is limited, which leads to a prolongeduseful life or service life of the methanol synthesis catalyst used inthe methanol pre-reactor.

The methanol main reactors can be operated in a water-cooled, gas-cooledor adiabatic manner. Due to the high reaction enthalpy in the methanolsynthesis, the cooled reactor operation is recommendable.

According to a preferred aspect of the invention two methanol mainreactors are present in the synthesis cycle, wherein the first methanolmain reactor in flow direction is operated in a water-cooled manner andthe second methanol main reactor in flow direction is operated in agas-cooled manner. As cooling gas, the synthesis gas entering into thesynthesis cycle can be used in the second methanol main reactor.

The invention also extends to a plant for the production of methanolfrom a synthesis gas containing hydrogen and carbon oxides with a highcontent of inert components, in particular for carrying out a processaccording to any of the preceding claims, with one or more methanolpre-reactors in which a first part of the carbon oxides is catalyticallyconverted to methanol, with one or more methanol main reactors in whicha further part of the carbon oxides is catalytically converted tomethanol, a separator downstream of the methanol pre-reactor orpre-reactors for separating the methanol from the synthesis gas, afurther separator downstream of the methanol main reactor or reactorsfor separating further methanol from the synthesis gas, and conduits forrecirculating a synthesis gas cycle stream to at least one methanol mainreactor. The plant according to the invention furthermore comprises aninert gas separation stage as well as conduits for supplying synthesisgas from the methanol main reactor or reactors to the inert gasseparation stage, conduits for discharging a purge stream from the inertgas separation stage, and conduits for recirculating a recirculationstream depleted of inert components to the methanol main reactor orreactors.

The invention furthermore relates to a method for retrofitting anexisting plant for the production of methanol with one or more methanolmain reactors within an inner synthesis cycle from the operation withsynthesis gas low in inerts to the operation with synthesis gas rich ininerts. The retrofitting method according to the invention comprises thefollowing measures:

-   -   Upstream of the first methanol main reactor a methanol        pre-reactor is provided.    -   Downstream of the last methanol main reactor an inert gas        separation stage is provided, and by recirculating a        recirculation stream depleted of inert components to the        methanol main reactor or reactors by means of corresponding        conduits an outer synthesis cycle is formed, wherein the        methanol pre-reactor or pre-reactors and the inert gas        separation stage are located outside the inner synthesis cycle.

In the plant for the methanol synthesis by a prior art process, which isschematically shown in FIG. 1 in a simplified form, a synthesis gasstream containing hydrogen and carbon oxides is supplied via conduit 1to a compressor 2 and by the same brought to the reaction pressure oftypically 5 to 10 MPa. Compressor 2 and compressor 15 can technically becoupled with each other. Via conduit 3, the compressed synthesis gasstream is supplied to a heat exchanger 4 and in the same brought to thereaction temperature, wherein the heat exchange mostly is effectedagainst the hot product gas stream from the synthesis reactor (not shownin FIG. 1). Via conduit 5, the preheated synthesis gas stream entersinto the methanol main reactor 6, where at temperatures between 200 and300° C. the partial conversion of hydrogen with carbon oxides iseffected on a copper-based methanol synthesis catalyst, wherein aproduct mixture is obtained, which contains methanol and non-convertedsynthesis gas. Various copper-based methanol synthesis catalysts arecommercially available, for example from Süd-Chemie AG, München. Thespace velocity in the synthesis reactor typically is 10000 to 30000 h⁻¹.In the schematic representation of FIG. 1, the methanol main reactor isshown as a one-stage reactor; preferably, however, a plurality ofseries-connected methanol main reactors are provided in the practicalconfiguration.

Via conduit 7, the product mixture is discharged from the methanol mainreactor. After cooling in the heat exchanger 8, where cooling totemperatures distinctly below the dew point for methanol and water,preferably between 30 and 60° C. is effected, the product mixture isdelivered via conduit 9 into the separator 10, where methanol isseparated as liquid, water-containing crude methanol and supplied to thefurther product processing via conduit 11. The gas product obtained inthe separator is discharged via conduit 12 and separated into a purgestream (purge), which is discharged via conduit 13, and a cycle stream,which is supplied to the cycle compressor 15 via conduit 14. Via thepurge stream, inert components are discharged from the process, but notin enriched form. Via conduit 16, the cycle stream is recirculated tothe synthesis reactor 6 and in this way a synthesis cycle is formed,wherein fresh synthesis gas is supplied via conduit 17 and combined withthe cycle stream. The ratio of the molar flow rates of cycle stream tofresh gas stream is referred to as cycle ratio.

In the plant shown in FIG. 2, which represents a preferred embodiment ofthe invention, the synthesis gas fresh gas stream initially is passedvia conduit 23 to a methanol pre-reactor 24. This is an adiabaticfixed-bed reactor filled with a granular, copper-based methanolsynthesis catalyst. Possibly, the synthesis gas must still be heated andcompressed before entry into the methanol pre-reactor, which is notshown in FIG. 2. The reactor inlet temperature into the methanolpre-reactor lies between 190 and 250° C., the reaction pressuretypically is 5 to 10 MPa. The space velocity in the methanol pre-reactortypically is 5000 to 15000 h⁻¹. There can be used the same catalyst typeof the copper-based methanol synthesis catalyst as in the methanol mainreactor; this has logistic advantages in operation of a plant by themethod according to the invention. It can, however, also be advantageousto use a copper-based methanol synthesis catalyst with a highersynthesis activity as compared to the methanol main reactor. Via conduit25, the product mixture is discharged from the methanol pre-reactor, inthe heat exchanger 26 cooled to temperatures distinctly below the dewpoint for methanol and water, preferably between 30 and 60° C., and viaconduit 27 supplied to a separator 28. In the same, methanol isseparated as liquid, water-containing crude methanol and via conduit 29supplied to the further product processing. Preferably, the furtherprocessing is effected along with the crude methanol obtained in theseparator 10 and discharged from the methanol main reactor via conduit11.

When the conversion of the synthesis gas to methanol in the methanolpre-reactor 24 is limited, it can be expedient to omit the heatexchanger 26 and the separator 28 and guide the synthesis gas containingonly a small amount of methanol directly to the methanol main reactorvia conduit 17.

As a further difference to the prior art process shown in FIG. 1, thepurge stream as shown in FIG. 2 is not discharged from the process viaconduit 13, but supplied to a pressure swing adsorption system 18. Themode of function and the operating conditions of such system are knownper se to the skilled person. In said system there is obtained asynthesis gas stream depleted of hydrogen and enriched in inertcomponents, which is removed from the process via conduit 19 (purge).Furthermore, there is obtained a synthesis gas stream enriched inhydrogen, which via conduit 20, compressor 21 and conduit 22 isrecirculated upstream of the methanol main reactor, whereby an outersynthesis cycle is formed.

FIG. 3 schematically shows a plant which represents a further preferredembodiment of the invention. This embodiment is preferred in particularwhen using coal-originating synthesis gas for the methanol synthesis,which can have a comparatively high methane content. In the gasificationof coal in the fixed bed a synthesis gas is obtained, which can containup to 60 vol-% of methane. In the plant shown in FIG. 3, as compared toFIG. 2, the purge stream leaving the pressure swing adsorption system 18is not removed from the process, but via conduit 30 supplied anautothermal reformer 31, in which the methane enriched in the purgestream is converted to further synthesis gas. The mode of function andthe operating conditions of the autothermal reformer also are known perse to the skilled person. A part of the product gas stream of theautothermal reformer is removed from the process as purge stream (purge)via conduit 19; a further part of the product gas stream of theautothermal reformer is supplied to the compressor 21 via conduit 32 andthereby joined with the synthesis gas stream supplied in conduit 20. Inthe conduit path 32 further processing stages not shown in the Figurecan be provided for the synthesis gas. Thus, it is possible to firstrecirculate the synthesis gas partial stream in conduit 32 to thepressure swing adsorption system 18, in order to separate the hydrogenand recirculate the same via conduit 20 to the methanol main reactor.The hydrogen content in the outer synthesis cycle thereby is increasedonce again.

With the invention an economic process for the production of methanolthus is proposed, which is characterized in that it is also possible toprocess synthesis gases with a high content of inert components. Incontrast to the processes proposed in the prior art, the processaccording to the invention is characterized by the absence of substancessuch as absorbents, which are foreign to the process or need to bedisposed of or regenerated. Further advantages include the technicalsimplicity, small apparatus sizes and conduit dimensions, savings ofcatalyst and a lower energy demand, for example for the requiredcompressor duty.

While the invention has been illustrated and described in detail in thedrawings and foregoing description, such illustration and descriptionare to be considered illustrative or exemplary and not restrictive. Itwill be understood that changes and modifications may be made by thoseof ordinary skill within the scope of the following claims. Inparticular, the present invention covers further embodiments with anycombination of features from different embodiments described above andbelow. Additionally, statements made herein characterizing the inventionrefer to an embodiment of the invention and not necessarily allembodiments.

The terms used in the claims should be construed to have the broadestreasonable interpretation consistent with the foregoing description. Forexample, the use of the article “a” or “the” in introducing an elementshould not be interpreted as being exclusive of a plurality of elements.Likewise, the recitation of “or” should be interpreted as beinginclusive, such that the recitation of “A or B” is not exclusive of “Aand B,” unless it is clear from the context or the foregoing descriptionthat only one of A and B is intended. Further, the recitation of “atleast one of A, B, and C” should be interpreted as one or more of agroup of elements consisting of A, B, and C, and should not beinterpreted as requiring at least one of each of the listed elements A,B, and C, regardless of whether A, B, and C are related as categories orotherwise. Moreover, the recitation of “A, B, and/or C” or “at least oneof A, B, or C” should be interpreted as including any singular entityfrom the listed elements, e.g., A, any subset from the listed elements,e.g., A and B, or the entire list of elements A, B, and C.

LIST OF REFERENCE NUMERALS

1 conduit

2 compressor

3 conduit

4 heat exchanger

5 conduit

6 methanol main reactor(s)

7 conduit

8 heat exchanger

9 conduit

10 separator

11-14 conduit

15 compressor

16-17 conduit

18 pressure swing adsorption system

19-20 conduit

21 compressor

22-23 conduit

24 methanol pre-reactor(s)

25 conduit

26 heat exchanger

27 conduit

28 separator

29-30 conduit

31 autothermal reformer

32 conduit

1 A process for the production of methanol from a synthesis gascomprising hydrogen, a carbon oxide, and an inert component, the processcomprising: (a) passing a first synthesis gas stream as feed streamthrough at least one methanol pre-reactor, in which a part of the carbonoxide is catalytically converted with hydrogen to obtain methanol; (b)separating off the methanol produced in (a) to obtain a second synthesisgas stream; c) passing the second synthesis gas stream, through at leastone methanol main reactor, in which a further part of the carbon oxideis catalytically converted with hydrogen to obtain methanol; d)separating off the methanol produced in c) to obtain a third synthesisgas stream; e) dividing the third synthesis gas stream into a fourthsynthesis gas stream and a fifth synthesis gas stream; f) recirculatingthe fourth synthesis gas stream to the methanol main reactor to form aninner synthesis cycle; g) supplying the fifth synthesis gas stream to atleast one inert gas separation stage, to obtain a sixth stream depletedof inert components and a purge stream enriched in inert components; g)recirculating the sixth stream to the methanol main reactor to form anouter synthesis cycle.
 2. The method of claim 1, wherein the inert gasseparation stage comprises a pressure swing adsorption system.
 3. Themethod of claim 1, wherein the inert gas separation stage comprises anautothermal reformer.
 4. The method of claim 1, wherein the firstsynthesis gas stream is obtained by gasification of natural gas with agas comprising oxygen.
 5. The method of claim 1, wherein the firstsynthesis gas stream is obtained by gasification of coal with a gascomprising oxygen.
 6. The method of claim 1, further comprising: (h)supplying the methanol obtained to further product processing.
 7. Themethod of claim 1, wherein the methanol main reactor is operated in awater-cooled manner.
 8. The method of claim 1, wherein the at least onemethanol main reactor comprises: a first methanol main reactor; and asecond methanol main reactor, wherein the first methanol main reactor inflow direction is operated in a water-cooled manner, and wherein thesecond methanol main reactor in flow direction is operated in agas-cooled manner.
 9. A plant for the production of methanol from asynthesis gas comprising hydrogen, a carbon, and an inert component, theplant comprising: a methanol pre-reactor in which a first part of thecarbon oxide is catalytically converted to methanol, a methanol mainreactor in which a further part of the carbon oxide is catalyticallyconverted to methanol; a separator downstream of the methanolpre-reactor suitable for separating the methanol from the synthesis gas;a further separator downstream of the methanol main reactor suitable forseparating further methanol from the synthesis gas, a conduit suitablefor recirculating a synthesis gas cycle stream to the one methanol mainreactor; an inert gas separation stage comprising (i) a conduit suitablefor supplying synthesis gas from the methanol main reactor to the inertgas separation stage, (ii) a conduit suitable for discharging a purgestream from the inert gas separation stage, and (iii) a conduit suitablefor recirculating a recirculation, stream depleted of inert componentsto the methanol main reactor.
 10. A method for retrofitting an existingmethanol production plant comprising a methanol main reactor within aninner synthesis cycle from operating with synthesis gas low in inerts tooperating with synthesis gas rich in inerts, the method comprising:providing a methanol pre-reactor upstream of a first methanol mainreactor; a providing an inert gas separation stage downstream of a lastmethanol main reactor, and recirculating a recirculation stream depletedof inert components to the methanol main reactor to form an outersynthesis cycle, wherein the methanol pre-reactor and the inert gasseparation stage are connected outside the inner synthesis cycle. 11 Themethod of claim 1, wherein the inert gas separation stage comprises amembrane system. 12 The method of claim 1, wherein the inert gasseparation stage comprises an autothermal reformer, jointly with apressure swing adsorption system. 13 The method of claim 1, wherein thefirst synthesis gas stream is obtained by gasification of biomass with agas comprising oxygen. 14 The method of claim 1, wherein the methanolmain reactor is operated in gas-cooled manner. 15 The method of claim 1,wherein the methanol main reactor is operated in an adiabatic manner. 16The method of claim 1, wherein the at least one methanol main reactorconsists essentially of: a first methanol main reactor; and a secondmethanol main reactor, wherein the first methanol main reactor in flowdirection is operated in a water-cooled manner, and wherein the secondmethanol main reactor in flow direction is operated in a gas-cooledmanner.